CN109071413A - Organic electroluminescent compounds and Organnic electroluminescent device comprising it - Google Patents

Organic electroluminescent compounds and Organnic electroluminescent device comprising it Download PDF

Info

Publication number
CN109071413A
CN109071413A CN201780024400.8A CN201780024400A CN109071413A CN 109071413 A CN109071413 A CN 109071413A CN 201780024400 A CN201780024400 A CN 201780024400A CN 109071413 A CN109071413 A CN 109071413A
Authority
CN
China
Prior art keywords
unsubstituted
substituted
aryl
alkyl
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780024400.8A
Other languages
Chinese (zh)
Other versions
CN109071413B (en
Inventor
吴洪世
金荣光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Electronic Materials Korea Ltd
Original Assignee
Rohm and Haas Electronic Materials Korea Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Electronic Materials Korea Ltd filed Critical Rohm and Haas Electronic Materials Korea Ltd
Priority claimed from PCT/KR2017/002959 external-priority patent/WO2017191896A1/en
Publication of CN109071413A publication Critical patent/CN109071413A/en
Application granted granted Critical
Publication of CN109071413B publication Critical patent/CN109071413B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C07C13/66—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings the condensed ring system contains only four rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This disclosure relates to organic electroluminescent compounds and the Organnic electroluminescent device comprising it.By using the organic electroluminescent compounds of the disclosure, the Organnic electroluminescent device with excellent luminance characteristic can be manufactured.

Description

Organic electroluminescent compounds and Organnic electroluminescent device comprising it
Technical field
This disclosure relates to organic electroluminescent compounds and the Organnic electroluminescent device comprising it.
Background technique
El light emitting device (EL device) is a kind of selfluminous device, has an advantage in that and provides broader view Angle, higher contrast ratio and faster response time.First organic el device is by Eastman Kodak Company (Eastman Kodak) It is developed as the material for being used to form luminescent layer by using small aromatic diamine molecule and aluminium complex [" using object Neo-Confucianism report (Appl.Phys.Lett.) " 51,913,1987].
In order to improve the efficiency and stability of organic el device, it has comprising hole injection layer, hole transmission layer, shines The structure of the multilayer of layer, electron transfer layer and electron injecting layer.Known to the selection of compound included in hole transmission layer Method to improve equipment energy characteristic (such as arriving the hole transport efficiency, luminous efficiency, service life of luminescent layer).
In this regard, copper phthalocyanine (CuPc), 4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl (NPB), N, N '-two Phenyl-N, N '-bis- (3- aminomethyl phenyls) (1,1 '-xenyl) -4, "-three (the 3- aminomethyl phenyl benzene of 4 '-diamines (TPD), 4,4 ', 4 Base amino) triphenylamine (MTDATA) etc. is used as hole injection and transmission material.However, using the organic el device of these materials There is the problem of quantum efficiency and service life.This is because when driving organic el device under high currents, in anode and sky There is thermal stress between the implanted layer of cave.The service life of thermal stress significant decrease described device.Further, since being injected for hole The organic material of layer has very high hole mobility, so hole-electron charge balance can be broken and quantum yield (Cd/A) it can reduce.
Therefore, there is still a need for developing the hole transmission layer for improving organic el device performance.
South Korea patent application Patent Publication KR 10-2015-0066202 discloses the benzene substituted with arylamino etc. And [b] fluorenes.However, the change that the bibliography replaces at the 5th carbon potential of benzo [b] fluorenes with no specific disclosure of arylamino etc. Close object.
International Publication case WO 20,15/,061,198 A also disclose with the substituted benzo such as arylamino [b] fluorenes.So And the bibliography is with no specific disclosure of the example for using the compound in hole transmission layer.In addition, the bibliography does not have The compound that open arylamino etc. replaces at the 5th carbon potential of benzo [b] fluorenes.
Summary of the invention
Problem to be solved
Purpose of this disclosure is to provide can be used for manufacturing with excellent life characteristic, since triplet energies are increased changing The organic electroluminescence hair of the Organnic electroluminescent device of kind luminous efficiency and/or the superior heat-stability reduced due to depositing temperature Optical compounds.
Issue-resolution
The inventors discovered that the 5th carbon potential by the Organic electroluminescent compound in the structure with benzo [b] fluorenes has Substituted base, luminous efficiency due to triplet energies increase and improve and/or thermal stability due to depositing temperature reduction and change It is kind.More specifically, object above can be realized by the organic electroluminescent compounds indicated by following formula 1:
Wherein
Ar1To Ar6(C1-C30) alkyl for being substituted or being unsubstituted is each independently represented, is substituted or is unsubstituted (C6-C30) aryl, 5 to 30 unit's heteroaryls for being substituted or being unsubstituted or the spiral shell [fluorenes-(C3- for being substituted or being unsubstituted C30) cycloalkanes] base；Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6Monocycle or polycyclic 3 to 30 yuan of rouge can be connected to each other to form Ring race ring or aromatic ring, the hetero atom that (one or more) carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced；
L1It indicates singly-bound, be substituted or (C6-C30) arlydene being unsubstituted or be substituted or be unsubstituted 5 to 30 First inferior heteroaryl；
L2It indicates singly-bound, be substituted or be unsubstituted (C1-C30) alkylidene, (the C6- that is substituted or is unsubstituted C30) arlydene or 5 to the 30 yuan of inferior heteroaryls for being substituted or being unsubstituted, condition are the L in the case where n is 02It is not present；
R1And R2Each independently represent hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted or (C6-C30) aryl for being unsubstituted is substituted or 5 to 30 unit's heteroaryls the being unsubstituted, (C3- for being substituted or being unsubstituted C30) naphthenic base, 3 to 7 membered heterocycloalkyls for being substituted or being unsubstituted, (C6-C30) aryl for being substituted or being unsubstituted (C1-C30) alkyl ,-NR11R12、-SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or may be connected to (one or It is multiple) adjacent substituents to be to form monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom The hetero atom that nitrogen, oxygen and sulphur can be selected from by least one is replaced；
R11To R17It each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted Or be unsubstituted (C6-C30) aryl, be substituted or 5 to 30 unit's heteroaryls being unsubstituted, be substituted or be unsubstituted 3 To 7 membered heterocycloalkyls or (C3-C30) naphthenic base for being substituted or being unsubstituted；Or it may be connected to that (one or more) is adjacent to be taken For Dai Ji to form monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom can be by least one A hetero atom displacement selected from nitrogen, oxygen and sulphur；
M indicates 1 to 2 integer, in the case where m is 2, NAr1Ar2Each of may be the same or different；
N indicates 0 to 2 integer, in the case where n is 2, NAr3Ar4Each of may be the same or different；
A indicates 1 to 5 integer, in the case where a is the integer of two or more, R1Each of may be the same or different；
B indicates 1 to 4 integer；In the case where b is the integer of two or more, R2Each of may be the same or different；
(Asia) heteroaryl contains at least one hetero atom for being selected from B, N, O, S, Si and P；And
Heterocyclylalkyl contains at least one hetero atom for being selected from O, S and N.
Effect of the invention
By using the organic electroluminescent compounds of the disclosure, can manufacture steady with excellent luminous efficiency and/or heat Qualitative Organnic electroluminescent device.In addition, due to the luminous efficiency and/or excellent heat stability of Organnic electroluminescent device, Therefore the relatively long service life of device can be realized.
Specific embodiment
Hereinafter, it will be described in the disclosure.It is intended to explain the disclosure however, being described below, and is not intended to appoint Where formula limits the scope of the present disclosure.
This disclosure relates to the organic electroluminescent compounds of formula 1, the electroluminescent organic material comprising the compound, with And the Organnic electroluminescent device comprising the material.
Term " organic electroluminescent compounds " in the disclosure refers to the chemical combination that can be used in Organnic electroluminescent device Object, and if desired, may include in any layer for constituting Organnic electroluminescent device.
Term " electroluminescent organic material " in the disclosure refers to the material that can be used in Organnic electroluminescent device, and It and may include at least one compound.If desired, electroluminescent organic material may include constituting Organnic electroluminescent device Any layer in.For example, electroluminescent organic material can assist material for hole-injecting material, hole mobile material, hole Material, shine auxiliary material, electron-blocking materials, luminescent material, electronics padded coaming, hole barrier materials, electron transport material Or electron injection material.
The electroluminescent organic material of the disclosure may include at least one compound indicated by formula 1.The change indicated by formula 1 Closing object may include in at least one layer for constituting Organnic electroluminescent device, and may include in the hair as phosphorescent light body material Photosphere and/or as in the hole transmission layer of hole mobile material, but not limited to this.
Hereinafter, the organic electroluminescent compounds indicated by formula 1 be will be described in.
Herein, " (C1-C30) (Asia) alkyl " means straight chain or the branch of 1 to 30 carbon atoms with chain is constituted Chain (Asia) alkyl, wherein the number of carbon atom is preferably 1 to 10, more preferably 1 to 6, and including methyl, ethyl, n-propyl, Isopropyl, normal-butyl, isobutyl group, tert-butyl etc.." (C2-C30) alkenyl " means with the straight of 2 to 30 carbon atoms for constituting chain Chain or branched chain alkene groups, wherein the number of carbon atom is preferably 2 to 20, and more preferably 2 to 10, and including vinyl, 1- third Alkenyl, 2- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 2- methyl but-2-ene base etc.." (C2-C30) alkynyl " is tool There are the straight chain or branched chain alkyne groups of 2 to 30 carbon atoms for constituting chain, wherein the number of carbon atom is preferably 2 to 20, more excellent Selection of land 2 to 10, and it is amyl- including acetenyl, 1- propinyl, 2-propynyl, 1- butynyl, 2- butynyl, 3- butynyl, 1- methyl 2- alkynyl etc.." (C3-C30) naphthenic base " is monocycle or polycyclic hydrocarbon with 3 to 30 ring backbone c atoms, wherein carbon atom Quantity is preferably 3 to 20, and more preferably 3 to 7, and including cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc.." 3 to 7 yuan miscellaneous Naphthenic base " is to be selected from at least one by B, N, O, S, Si and P, the preferably hetero atom and 3 to 7 of the group of O, S and N composition The naphthenic base of ring backbone atoms, and including tetrahydrofuran, pyrrolidines, tiacyclopentane, oxinane etc.." (C6-C30) (Asia) Aryl " be derived from 6 to 30 ring backbone c atoms aromatic hydrocarbon monocycle or condensed ring, middle ring backbone c atoms Number is preferably 6 to 20, more preferably 6 to 15, and as specific example include phenyl, xenyl, terphenyl, naphthalene, Binaphthyl, phenyl napthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo fluorenyl, dibenzo fluorenyl, phenanthryl, phenyl phenanthryl, anthracene Base, indenyl, triphenylene, pyrenyl, aphthacene base, base, Qu Ji, thick four benzene base, fluoranthene base etc.." 5 to 30 yuan of (Asia) heteroaryls Base " be at least one, preferably 1 to 4 selected from by B, N, O, S, Si and P group formed hetero atoms and 5 to 30 rings The aryl of backbone atoms, the number of middle ring backbone atoms are preferably 5 to 20, and more preferably 5 to 15；For monocycle or at least The condensed condensed ring of one phenyl ring；It can fractional saturation；It can be for by keeping at least one heteroaryl or aryl single through (one or single) It is keyed to heteroaryl and is formed by group；And including monocyclic heteroaryl, including furyl, thienyl, pyrrole radicals, imidazoles Base, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazoles base, triazine radical, tetrazine base, three Oxazolyl, tetrazole radical, furan a word used for translation base, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl etc. and condensed ring type heteroaryl, including benzo furan It mutters base, benzothienyl, isobenzofuran-base, dibenzofuran group, dibenzothiophene, benzo aphthothiophenes base, benzo miaow Oxazolyl, benzothiazolyl, benzisothia oxazolyl, benzo isoxazolyl, benzoxazolyl, isoindolyl, indyl, indazolyl, Diazosulfide base, quinolyl, isoquinolyl, cinnoline base, quinazolyl, quinoxalinyl, carbazyl, coffee oxazines base, coffee piperidinyl, Benzodioxole group etc.." halogen " includes F, Cl, Br and I.
The compound of formula 1 can be indicated by following formula 2 or 3:
Wherein Ar1To Ar6、L1、L2、R1、R2, a, b, m and n be as defined in formula 1.
Herein, " being substituted " stated in " be substituted or be unsubstituted " means the hydrogen atom in a certain functional group It is replaced by another atom or another functional group's (i.e. substituent group).Ar in formula 11To Ar6、L1、L2、R1、R2And R11To R17 In (Asia) alkyl being substituted, (Asia) aryl being substituted, (Asia) heteroaryl being substituted, the naphthenic base being substituted, through taking The substituent group of the Heterocyclylalkyl in generation, the aryl alkyl being substituted and the spiral shell being substituted [fluorenes-(C3-C30) cycloalkanes] base is respectively independent Ground be selected from least one of the group being made up of: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, Halogenated (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio group, (C3- C30) naphthenic base, (C3-C30) cycloalkenyl, 3 to 7 membered heterocycloalkyls, (C6-C30) aryloxy group, (C6-C30) arylthio, without taking Generation or 3 to 30 unit's heteroaryls replaced through (C6-C30) aryl, (C6-C30) that is unsubstituted or replaces through 3 to 30 unit's heteroaryls Aryl, three (C1-C30) alkyl tin groups, alkyl silane groups, three (C6-C30) aryl-silane bases, two (C1-C30) alkyl (C6-C30) aryl-silanes Base, two (C6-C30) aryl-silane base of (C1-C30) alkyl, amino, list or two (C1-C30) alkyl aminos, list or two (C6- C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkyl-carbonyl, (C1-C30) alkoxy carbonyl Base, (C6-C30) aryl carbonyl, two (C6-C30) aryl boryls, two (C1-C30) alkyl boryls, (C1-C30) alkyl (C6- C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl；And it is preferably each From independently being (C1-C6) alkyl or (C6-C20) aryl.
In equation 1 above, Ar1To Ar6It each independently represents (C1-C30) alkyl for being substituted or being unsubstituted, be substituted Or it (C6-C30) aryl for being unsubstituted, 5 to 30 unit's heteroaryls for being substituted or being unsubstituted or is substituted or is unsubstituted Spiral shell [fluorenes-(C3-C30) cycloalkanes] base；Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6Monocycle or polycyclic can be connected to each other to form 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom can be selected from the miscellaneous original of nitrogen, oxygen and sulphur by least one Son displacement.
Preferably, Ar1To Ar4It each independently represents (C6-C25) aryl for being substituted or being unsubstituted, be substituted or not 5 to 15 unit's heteroaryls being substituted or the spiral shell for being substituted or being unsubstituted [fluorenes-(C5-C8) cycloalkanes] base, and it is highly preferred that Ar1 to Ar4 each independently represents (C6-C25) virtue for being unsubstituted or replacing through (C1-C6) alkyl or (C6-C20) aryl Base；5 to 15 unit's heteroaryls for being unsubstituted or replacing through (C1-C6) alkyl or (C6-C12) aryl；Spiral shell [the fluorenes-being unsubstituted Pentamethylene] base；Or spiral shell [fluorenes-hexamethylene] base being unsubstituted.Specifically, Ar1 to Ar4 can each independently represent phenyl, Xenyl, terphenyl, through (one or more) methyl substituted fluorenyl, through (one or more) phenyl replace fluorenyl, warp (one or more) methyl substituted benzo fluorenyl, naphthylphenyl, the phenyl replaced through fluorenes, the pyridyl group replaced through phenyl, two Benzofuranyl, dibenzothiophene, through (one or more) methyl substituted bisbenzothiazole base, through (one or more) benzene Bisbenzothiazole base, spiral shell [fluorenes-pentamethylene] base, spiral shell [fluorenes-hexamethylene] base that base replaces etc..
Preferably, Ar5And Ar6It each independently represents (C1-C6) alkyl for being substituted or being unsubstituted or is substituted or not (C6-C12) aryl being substituted；Or monocycle or polycyclic 5 to 15 yuan of aliphatic rings or aromatic ring can be connected to each other to form, and And it is highly preferred that Ar5And Ar6(C1-C6) alkyl being unsubstituted is each independently represented, or (C6-C12) virtue being unsubstituted Base；Or 5 to 15 yuan of aliphatic rings of monocycle can be connected to each other to form.Specifically, Ar5And Ar6First can be each independently represented Base, phenyl etc., or spiro cyclopentane can be connected to each other to form.
L1It indicates singly-bound, be substituted or (C6-C30) arlydene being unsubstituted or be substituted or be unsubstituted 5 to 30 First inferior heteroaryl, preferably expression singly-bound, (C6-C20) arlydene for being substituted or being unsubstituted are substituted or are unsubstituted 5 to 15 yuan of inferior heteroaryls, and more preferably indicate singly-bound, (C6-C20) arlydene being unsubstituted or be unsubstituted 5 To 15 yuan of inferior heteroaryls.Specifically, L1It can indicate that singly-bound, phenylene, naphthylene, biphenylene, naphthylphenylene, pyridine are sub- Phenyl, sub-pyridyl group, phenyl sub-pyridyl group, sub- bipyridyl, dibenzo furylidene, dibenzo Asia thienyl etc..
L2It indicates singly-bound, be substituted or be unsubstituted (C1-C30) alkylidene, (the C6- that is substituted or is unsubstituted C30) arlydene or 5 to the 30 yuan of inferior heteroaryls for being substituted or being unsubstituted, condition are the L in the case where n is 02It is not present.L2 Preferably indicate singly-bound or (C6-C12) arlydene for being substituted or being unsubstituted, and preferably indicate singly-bound or be substituted or (C6-C12) arlydene being unsubstituted.Specifically, L2It can indicate singly-bound, phenylene etc..
R1And R2Each independently represent hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted or (C6-C30) aryl for being unsubstituted is substituted or 5 to 30 unit's heteroaryls the being unsubstituted, (C3- for being substituted or being unsubstituted C30) naphthenic base, 3 to 7 membered heterocycloalkyls for being substituted or being unsubstituted, (C6-C30) aryl for being substituted or being unsubstituted (C1-C30) alkyl ,-NR11R12、-SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or may be connected to (one or It is multiple) adjacent substituents to be to form monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom The hetero atom that nitrogen, oxygen and sulphur can be selected from by least one is replaced, and is preferably each independently represented hydrogen or is substituted or without taking (C6-C15) aryl in generation, and (C6-C15) aryl for more preferably each independently representing hydrogen or being unsubstituted.It is specific next It says, R1And R2Hydrogen, xenyl etc. can be each independently represented.
R11To R17It each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted Or be unsubstituted (C6-C30) aryl, be substituted or 5 to 30 unit's heteroaryls being unsubstituted, be substituted or be unsubstituted 3 To 7 membered heterocycloalkyls or (C3-C30) naphthenic base for being substituted or being unsubstituted；Or it may be connected to that (one or more) is adjacent to be taken For Dai Ji to form monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom can be by least one A hetero atom displacement selected from nitrogen, oxygen and sulphur.
According to one embodiment of the disclosure, in equation 1 above, Ar1To Ar4Each independently represent be substituted or without (C6-C25) aryl for replacing is substituted or 5 to 15- unit's heteroaryls being unsubstituted or the spiral shell [fluorenes-for being substituted or being unsubstituted (C5-C8) cycloalkanes] base；Ar5And Ar6It each independently represents (C1-C6) alkyl for being substituted or being unsubstituted or is substituted or not (C6-C12) aryl being substituted；Or monocycle or polycyclic 5 to 15 yuan of aliphatic rings or aromatic ring can be connected to each other to form；L1 It indicates singly-bound, be substituted or (C6-C20) arlydene being unsubstituted or 5 to the 15 yuan of inferior heteroaryls for being substituted or being unsubstituted； L2(C6-C12) arlydene for indicating singly-bound or being substituted or being unsubstituted, condition are the L in the case where n is 02It is not present；And And R1And R2(C6-C15) aryl for each independently representing hydrogen or being substituted or being unsubstituted.
According to another embodiment of the present disclosure, in equation 1 above, Ar1To Ar4It each independently represents and is unsubstituted or passes through (C1-C6) (C6-C25) aryl that alkyl or (C6-C20) aryl replace；It is unsubstituted or through (C1-C6) alkyl or (C6-C12) 5 Dao the 15- unit's heteroaryls that aryl replaces；Spiral shell [fluorenes-pentamethylene] base being unsubstituted；Or the spiral shell [fluorenes-hexamethylene] being unsubstituted Base；Ar5And Ar6(C6-C12) aryl for each independently representing (C1-C6) alkyl being unsubstituted or being unsubstituted；But or that This connection is to form 5 to 15 yuan of aliphatic rings of monocycle；L1 indicates singly-bound, (C6-C20) arlydene being unsubstituted or is unsubstituted 5 to 15 yuan of inferior heteroaryls；L2 indicates singly-bound or (C6-C12) arlydene for being unsubstituted, condition be in the case where n is 0, L2 is not present；And (C6-C15) aryl that R1 and R2 each independently represent hydrogen or be unsubstituted.
Include following compound by the organic electroluminescent compounds that formula 1 indicates, but be not limited to this:
The organic electroluminescent compounds of the disclosure can be prepared by synthetic method well known by persons skilled in the art.Citing For, it can be prepared according to following reaction process.
[reaction process 1]
[reaction process 2]
[reaction process 3]
Wherein Ar1To Ar6、L1、L2、R1、R2, a, b, m and n as defined in formula 1, and X indicate halogen.
The disclosure provides the electroluminescent organic material of the organic electroluminescent compounds comprising formula 1, and comprising described The Organnic electroluminescent device of material.
Above-mentioned material can be the material of main part of luminescent layer, specifically emit the main body material of the Organnic electroluminescent device of feux rouges Material.Above-mentioned material can be hole mobile material, specifically emit the hole mobile material of the Organnic electroluminescent device of feux rouges.When There are when two or more hole transmission layers, material can be included in the biography of the hole in the hole transmission layer adjacent with luminescent layer Defeated material.
Above-mentioned material can be only by constituting according to the organic electroluminescent compounds of the disclosure, or can further comprise Organic Electricity Usually used conventional material in electroluminescent material.
Organnic electroluminescent device includes first electrode；Second electrode；Between the first and second electrodes at least one A organic layer.Organic layer may include the organic electroluminescent compounds of at least one formula 1.
One in first and second electrodes can be anode, and another can be cathode.Organic layer may include luminescent layer, And it can further include at least one and be selected from hole injection layer, hole transmission layer, hole auxiliary layer, luminous auxiliary layer, electronics Transport layer, electron buffer layer, electron injecting layer, middle layer, hole blocking layer and electronic barrier layer layer.
The organic electroluminescent compounds of the disclosure may include auxiliary in luminescent layer, hole injection layer, hole transmission layer, hole Help layer, shine auxiliary layer, electron transfer layer, electron buffer layer, electron injecting layer, middle layer, hole blocking layer and electronic blocking In at least one layer in layer, in at least one layer preferably in luminescent layer and hole transmission layer.When there are two or more When luminescent layer or hole transmission layer, organic electroluminescent compounds can be used at least one layer.When in hole transmission layer When, the organic electroluminescent compounds of the disclosure can be used as hole mobile material by comprising.When there are two or more holes When transport layer, the compound of the disclosure may include in the hole transmission layer adjacent with luminescent layer.When in luminescent layer, this Disclosed organic electroluminescent compounds can be used as material of main part by comprising.
According to one embodiment of the disclosure, the organic electroluminescent compounds of the disclosure can be used as hole mobile material, And it can provide with excellent lifetime characteristic, due to the increased improved luminous efficiency of triplet energies and/or due to deposition temperature Spend the Organic electroluminescent device of reduced superior heat-stability.
Organic electroluminescent compounds comprising the disclosure can be further as the Organnic electroluminescent device of material of main part Comprising one or more host compounds other than the organic electroluminescent compounds of the disclosure, and can further include One or more dopants.
When the disclosure organic electroluminescent compounds as luminescent layer material of main part (the first material of main part) by comprising When, another compound can be used as the second material of main part by comprising.In herein, the first material of main part and the second material of main part Weight ratio in the range of 1: 99 to 99: 1.
The material of main part of compound other than the organic electroluminescent compounds of the disclosure can be any of master Body.Can be used as in the case where the compound of the disclosure is used as hole mobile material the material of main part of luminescent layer by comprising chemical combination Object, and the compound of the disclosure be used as material of main part in the case where can be used as the second material of main part by comprising compound, If they are selected from the group being made of the compound that the following Expression 11 to 16 indicates, for luminous efficiency, they can be excellent Choosing:
H-(Cz-L4)h-M-----------(11)
H-(Cz)i-L4-M-----------(12)
Wherein
Cz is indicated with flowering structure:
A expression-O- or-S-；And
R21To R24It each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted Or be unsubstituted (C6-C30) aryl, be substituted or (5 to the 30 yuan) heteroaryl being unsubstituted or-SiR25R26R27；Wherein R25 To R27Each independently represent (C1-C30) alkyl for being substituted or being unsubstituted or (C6-C30) that is substituted or is unsubstituted Aryl；L4It indicates singly-bound, be substituted or (C6-C30) arlydene being unsubstituted or (5 to 30 yuan) that are substituted or are unsubstituted Inferior heteroaryl；M indicates (C6-C30) aryl for being substituted or being unsubstituted or (5 to the 30 yuan) heteroaryl for being substituted or being unsubstituted Base；Y1And Y2Each independently represent-O- ,-S- ,-NR31Or-CR32R33, condition is Y1And Y2It does not exist simultaneously；R31To R33Respectively From (C1-C30) alkyl for independently indicating to be substituted or be unsubstituted, (C6-C30) aryl or warp that are substituted or are unsubstituted (5 to the 30 yuan) heteroaryl for replacing or being unsubstituted；R32And R33It may be the same or different；H and i each independently represent 1 to 3 Integer；J, k, l and m each independently represent 0 to 4 integer；Wherein if g, h, i, j, k, 1 and m indicate two or more it is whole Number, then each (Cz-L4), each (Cz), each R21, each R22, each R23Or each R24It may be the same or different；
Wherein
Y3To Y5Each independently represent CR34Or N, preferably wherein at least one is N；
R34Expression hydrogen, (C1-C30) alkyl for being substituted or being unsubstituted, (C6-C30) virtue for being substituted or being unsubstituted Base or (5 to the 30 yuan) heteroaryl for being substituted or being unsubstituted；
B1And B2It each independently represents hydrogen, (C6-C30) aryl that is substituted or is unsubstituted or be substituted or without taking (5 to the 30 yuan) heteroaryl in generation；
B3Indicate (C6-C30) aryl for being substituted or being unsubstituted or (5 to the 30 yuan) heteroaryl for being substituted or being unsubstituted Base；And
L5It indicates singly-bound, be substituted or (C6-C30) arlydene being unsubstituted or be substituted or be unsubstituted (5 to 30 Member) inferior heteroaryl.
Specifically, the example of the second material of main part is as follows, but not limited to this.
[wherein TPS indicates tri-phenyl-silane base]
It is preferably at least one phosphorescent dopants in the Organnic electroluminescent device of the disclosure according to the dopant for including. It is applied to and is not particularly limited according to the phosphorescent dopant material of the Organnic electroluminescent device of the disclosure, but be preferably selected from Iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) metallization complex compound, it may be more preferable to ground be selected from iridium (Ir), osmium (Os), The ortho-metalated complex compound of copper (Cu) and platinum (Pt), and can be even more preferably ortho-metalated iridium complexingization Close object.
It include that dopant in the Organnic electroluminescent device of the disclosure is preferably selected from by following formula 101 to 104 The group of compound composition, but not limited to this.
Wherein L is selected from flowering structure:
R100、R134And R135Each independently represent hydrogen, deuterium, (C1-C30) alkyl for being substituted or being unsubstituted or through taking Generation or (C3-C30) naphthenic base being unsubstituted；
R101To R109And R111To R123Each independently represent hydrogen, deuterium, the halogen, (C1- for being unsubstituted or replacing through halogen C30) alkyl, (C3-C30) naphthenic base for being substituted or being unsubstituted, (C6-C30) aryl, the cyano that are substituted or are unsubstituted Or (C1-C30) alkoxy for being substituted or being unsubstituted；R106To R109Adjacent substituents can connect to each other to form and be substituted Or the condensed ring being unsubstituted, such as be unsubstituted or through alkyl-substituted fluorenes, be unsubstituted or through alkyl-substituted dibenzo thiophene Pheno is unsubstituted or through alkyl-substituted dibenzofurans；Or R120To R123Adjacent substituents can connect to each other to form through The condensed ring for replacing or being unsubstituted, such as the quinoline for being unsubstituted or replacing through alkyl or aryl；
R124To R133And R136To R139Each independently represent hydrogen, deuterium, halogen, (C1-C30) for being substituted or being unsubstituted Alkyl or (C6-C30) aryl for being substituted or being unsubstituted；And R124To R127Adjacent substituents can connect to each other to form The condensed ring for being substituted or being unsubstituted, for example, be unsubstituted or through alkyl-substituted fluorenes, be unsubstituted or through alkyl-substituted two Benzothiophene is unsubstituted or through alkyl-substituted dibenzofurans；
X indicates CR11R12, O or S；
R11And R12It each independently represents (C1-C10) alkyl for being substituted or being unsubstituted or is substituted or is unsubstituted (C6-C30) aryl；
R201To R211Each independently represent hydrogen, deuterium, halogen, be unsubstituted or through halogen replace (C1-C30) alkyl, (C3-C30) naphthenic base for being substituted or being unsubstituted or (C6-C30) aryl for being substituted or being unsubstituted；And R208To R211 Adjacent substituents can connect to each other to form the condensed ring for being substituted or being unsubstituted, such as be unsubstituted or through alkyl-substituted Fluorenes is unsubstituted or through alkyl-substituted dibenzothiophenes or is unsubstituted or through alkyl-substituted dibenzofurans；
F and g each independently represents 1 to 3 integer；In the case where f or g is the integer of two or more, each R100It can It is identical or different；And
S indicates 1 to 3 integer.
The specific example of dopant compound is as follows:
In another embodiment of the disclosure, the composition for being used to prepare Organnic electroluminescent device is provided, preferably Ground is used to prepare the composition of the Organnic electroluminescent device of transmitting feux rouges.Composition is preferably used for preparing organic electroluminescent The luminescent layer or hole transmission layer of device, and include the compound of the disclosure.When there are two or more hole transmission layers When, the compound of the disclosure may include in the composition for being used to prepare the hole transmission layer adjacent with luminescent layer.
In addition, including first electrode according to the Organnic electroluminescent device of the disclosure；Second electrode；With at first and second At least one organic layer between electrode.Organic layer includes luminescent layer, and luminescent layer may include being used to prepare according to the disclosure Organnic electroluminescent device composition.
In addition to the organic electroluminescent compounds indicated by formula 1, may be used also according to the Organnic electroluminescent device of the disclosure Further include at least one chemical combination selected from the group being made of Amines and styryl Amines Object.
In the Organnic electroluminescent device of the disclosure, in addition to the organic electroluminescent compounds of formula 1, organic layer may be used also Further include at least one metal selected from the group being made up of: the 1st race's metal, the group II metal, the 4th week of periodic table Phase transition metal, the 5th row transition metals, lanthanide series and d- transition elements organic metal, or include the metal At least one complex compound.
In addition, the Organnic electroluminescent device of the disclosure can be emitted and further including at least one luminescent layer it is white Light, the luminescent layer include blue, red or green electroluminescent as known in the art in addition to the compound of the disclosure Close object.If desired, it can further include yellow or orange light emitting layer.
In the Organnic electroluminescent device of the disclosure, it is preferable that selected from chalcogenide layer, metal halide and At least one layer (below is " superficial layers ") of metal oxide layer can be placed in (one or more of one or two electrode It is a) on inner surface.Specifically, chalcogenide (including oxide) layer of silicon or aluminium is preferably rested among electroluminescent On the anode surface of layer, and metal halide or metal oxide layer are preferably rested in the cathode of electroluminescent middle layer On surface.This kind of superficial layer provides operational stability for Organnic electroluminescent device.Preferably, chalcogenide includes SiOX(1 ≤X≤2)、AlOX(1≤X≤1.5), SiON, SiAlON etc.；Metal halide includes LiF, MgF2、CaF2, rare earth metal fluorination Object etc.；And metal oxide includes Cs2O、Li2O, MgO, SrO, BaO, CaO etc..
Between anode and luminescent layer, hole injection layer, hole transmission layer, electronic barrier layer or combinations thereof can be used.It is empty Cave implanted layer can be multilayer, to reduce from anode to hole transmission layer or the hole of electronic barrier layer injection barrier (or hole Injecting voltage), wherein each of described multilayer uses two kinds of compounds simultaneously.Hole transmission layer or electronic barrier layer can also For multilayer.
Between luminescent layer and cathode, electron buffer layer, hole blocking layer, electron transfer layer, electron injecting layer can be used Or combinations thereof.Electron buffer layer can be multilayer, to control the injection of electronics and to improve between luminescent layer and electron injecting layer Interfacial characteristics, wherein each of described multilayer can be used simultaneously two kinds of compounds.Hole blocking layer or electron transfer layer can also For multilayer, wherein polycompound can be used in each of described multilayer.
Luminous auxiliary layer can be placed between anode and luminescent layer, or be placed between cathode and luminescent layer.It is auxiliary when shining When layer being helped to be placed between anode and luminescent layer, it can be used for promoting hole injection and/or hole transport, or for preventing electronics It overflows.When luminous auxiliary layer is placed between cathode and luminescent layer, it can be used for promoting electron injection and/or electron-transport, Or for preventing hole from overflowing.Moreover, hole auxiliary layer can be placed in hole transmission layer (or hole injection layer) and luminescent layer it Between, and can be effectively facilitated or stop hole transport rate (or hole injection rate), to realize that charge balance is controlled System.In addition, electronic barrier layer can be placed between hole transmission layer (or hole injection layer) and luminescent layer, and blocking can be passed through The electronics for carrying out light emitting layer overflows and exciton is limited in luminescent layer, to prevent the leakage that shines.When organic electroluminescent fills When setting including two or more hole transmission layers, also included hole transmission layer can be used as hole auxiliary layer or electronic blocking Layer.Hole auxiliary layer and electronic barrier layer can have the effect of improving the efficiency of Organnic electroluminescent device and/or service life.
Preferably, in the Organnic electroluminescent device of the disclosure, electron transport compound and reproducibility dopant it is mixed The mixed zone for closing area or hole transport compound and oxidisability dopant can be placed at least one surface of a pair of electrodes.? In this case, electron transport compound is reduced into anion, and therefore become easier to injection electronics and by its from Mixed zone is transferred to luminescence medium.In addition, hole transport compound is oxidized to cation, and therefore become easier to inject Hole and it is transferred to electroluminescent medium from mixed zone.Preferably, oxidisability dopant include various lewis acids and Acceptor compound；And reproducibility dopant includes alkali metal, alkali metal compound, alkaline-earth metal, rare earth metal and its mixing Object.Reproducibility dopant layer can be used as charge generation layer, is used to prepare with two or more luminescent layers and emits white light Organic el device.
In order to formed constitute the disclosure organic el device each layer, can be used dry type film build method, as vacuum deposition, Sputter, plasma, ion plating method etc. or wet type film build method, such as spin coating, dip-coating, flow coating processes.
When using wet type membrane formation, by by the material for constituting each layer be dissolved or dispersed in suitable solvent (such as ethyl alcohol, Chloroform, tetrahydrofuran, dioxanes etc.) in formed film.Solvent is not particularly limited, as long as constituting the material of each layer described molten Be in agent it is soluble or dispersible, this will not cause any problem in forming layer.
By using the Organnic electroluminescent device of the disclosure, can manufacture for example for smart phone, tablet computer, pen Remember the display system of this computer, PC, TV or vehicle or lighting system such as indoor or outdoors lighting system.
Hereinafter, representative compound reference collapsed, is described in detail the organic electroluminescent compounds of the disclosure The characteristics of luminescence of preparation method, the physical characteristic of compound and the Organnic electroluminescent device comprising compound.
Example 1: prepare compound C-4
Prepare compound 1-1
By 100g indone (757mmol), 111.6g phthaladehyde (832mmol), 20% alcohol sodium alcohol solution of 10.3g (151mmol) and 1300mL ethyl alcohol are introduced into reaction vessel.After mixture is flowed back 2 hours, mixture is cooled to room temperature simultaneously It is stirred overnight.Reaction solution is cooled to 0 DEG C, and the solid being separated by filtration and is washed with cold methanol and hexane, 95gization is obtained Close object 1-1 (yield: 55%).
Prepare compound 1-2
33.3g iodine (144mmol), 44g hypophosphorous acid (660mmol, 50% aqueous solution) and 2000mL acetic acid are introduced and reacted In container, and mixture is stirred 30 minutes at 80 DEG C.95g compound 1-1 (413mmol) is slowly added dropwise thereto, and will Mixture is stirred overnight under reflux.The solid that reaction solution is cooled to room temperature, and is separated by filtration, and with cold methanol and oneself Alkane washing, obtains 73g compound 1-2 (yield: 82%).
Prepare compound 1-3
By 30g compound 1-2 (139mmol), 39g potassium hydroxide (694mmol), 2.3g potassium iodide (14mmol), 1.58g Benzyltriethylammoinium chloride (7mmol), 70mL distilled water and 700mL dimethyl sulfoxide are introduced into reaction vessel, and by mixture It is stirred at room temperature 30 minutes.49g methyl iodide (347mmol) is added thereto and is stirred at room temperature overnight mixture.With Ethyl acetate diluting reaction solution is simultaneously washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.Use Rotary Evaporators Solvent is removed, and products therefrom is purified by column chromatography, obtains 34g compound 1-3 (yield: 68%).
Prepare compound 1-4
3g compound 1-3 (12mmol) is dissolved in 50mL methylene chloride in the reaction vessel.By 1.3g bromine (16mmol) is dissolved in 10mL methylene chloride and is added in reaction solution.Mixture is stirred at room temperature 2 hours.With two Chloromethanes diluting reaction solution is simultaneously washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.It is removed with rotary evaporator The solid for removing solvent, and being separated by filtration, and washed with cold methanol, obtain 1.8g compound 1-4 (yield: 45%).
Compound 1-4 can also be obtained as follows:
By 1.3g compound 1-3 (5mmol), 10mL dimethylformamide and 1.23g N-bromosuccinimide (7mmol) is introduced into reaction vessel, and mixture is stirred at room temperature overnight.With ethyl acetate diluting reaction solution and with steam Distilled water washing.Then with the organic layer of the dry extraction of magnesium sulfate.Solvent is removed with rotary evaporator, and what is be separated by filtration consolidates Body, and washed with cold methanol, obtain 620mg compound 1-4 (yield: 36%).
Prepare compound C-4
By 10g compound 1-4 (31mmol), 13.7g it is bis- -9,9- dimethyl -9H- fluorenes -2- base amine (31mmol), 1.46g Tris(dibenzylideneacetone) dipalladium (0) (2mmol), 2.2mL tri-tert-butylphosphine (6mmol, 50% toluene solution), the 5.9g tert-butyl alcohol Sodium (62mmol) and 223mL toluene are introduced into reaction vessel, and mixture is flowed back 4 hours.Reaction solution is cooled to room temperature. With Rotary Evaporators remove solvent, and products therefrom by column chromatography purifying, obtain 10.5g compound C-4 (yield: 52%).The property of compound C-4 is shown in Table 1.
Example 2: prepare compound C-5
By 40g compound 1-4 (124mmol), 44.7gN-1,1 '-xenyl -4- base -9,9- dimethyl -9H- fluorenes -2- amine (124mmol), 3.4g tris(dibenzylideneacetone) dipalladium (0) (4mmol), (7mmol, 50% toluene are molten for 3mL tri-tert-butylphosphine Liquid), 17.8g sodium tert-butoxide (186mmol) and 600mL toluene is introduced into reaction vessel, and mixture flowed back 3 hours.It will be anti- Solution is answered to be cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 37.8gization Close object C-5 (yield: 51%).The property of compound C-5 is shown in Table 1.
Example 3: prepare compound C-7
By 10g compound 1-4 (31mmol), 16.5gN-1,1 '-xenyl -4- base -9,9- dimethyl -9H- fluorenes -2- amine (34mmol), 1.4g tris(dibenzylideneacetone) dipalladium (0) (2mmol), (3mmol, 50% toluene are molten for 1.2mL tri-tert-butylphosphine Liquid), 5.9g sodium tert-butoxide (62mmol) and 600mL toluene is introduced into reaction vessel, and mixture flowed back 3 hours.It will reaction Solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 11g compound C-7 (yield: 49%).The property of compound C-7 is shown in Table 1.
Example 4: prepare compound C-73
Prepare compound 2-1
By bromo- 11,11- dimethyl -11H- benzo [b] fluorenes (31mmol) of the 2- of 10g, 10mL dimethylformamide and 7.2g N-bromosuccinimide (40mmol) be introduced into reaction vessel, and mixture is stirred at room temperature overnight.With acetic acid second Ester diluting reaction solution is simultaneously washed with distilled water.Then with the organic layer of the dry extraction of magnesium sulfate.It is removed with rotary evaporator molten Agent, and the solid being separated by filtration, and washed with cold methanol, obtain 10.5mg compound 2-1 (yield: 84%).
Prepare compound C-73
By 10g compound 2-1 (25mmol), 15.6gN-1,1 '-xenyl -4- base -9,9- diphenyl -9H- fluorenes -2- amine (55mmol), 2.3g tris(dibenzylideneacetone) dipalladium (0) (2.5mmol), (5mmol, 50% toluene are molten for 2mL tri-tert-butylphosphine Liquid), 9.6g sodium tert-butoxide (99mmol) and 240mL toluene is introduced into reaction vessel, and mixture flowed back 3 hours.It will reaction Solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 9.6g compound C-73 (yield: 47%).The property of compound C-73 is shown in Table 1.
Example 5: prepare compound C-10
By 9,9- dimethyl-N-(4- (naphthalene -2- base) phenyl) -9H- fluorenes -2- of 7.4g compound 1-4 (23mmol), 9.4g Amine (23mmol), 1.05g tris(dibenzylideneacetone) dipalladium (0) (1.15mmol), 1.2mL tri-tert-butylphosphine (2.3mmol, 50% toluene solution), 4.4g sodium tert-butoxide (46mmol) and 200mL toluene be introduced into reaction vessel, and by mixture at 80 DEG C Lower reflux 3 hours.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom passes through column chromatography Purifying, obtains 3.7g compound C-10 (yield: 25%).The property of compound C-10 is shown in Table 1.
Example 6: prepare compound C-91
By 10g compound 1-4 (31mmol), 14.0g N- (9,9- dimethyl -9H- fluorenes -2- base) -11,11 '-dimethyl - 11H- benzo [b] fluorenes -2- amine (31mmol), 1.42g tris(dibenzylideneacetone) dipalladium (0) (1.60mmol), the tertiary fourth of 1.6mL tri- Base phosphine (3.1mmol, 50% toluene solution), 5.9g sodium tert-butoxide (62mmol) and 155mL toluene are introduced into reaction vessel, and will Mixture flows back 16 hours at 80 DEG C.Reaction solution is cooled to room temperature.Solvent is removed with rotary evaporator, and gained produces Object is purified by column chromatography, obtains 9.1g compound C-91 (yield: 42%).The property of compound C-91 is shown in Table 1.
Example 7: prepare compound C-92
By 8g compound 1-4 (25mmol), 11.9g N- ([1,1 ': 4 ', 1 "-tert-butyl] -4- base) -9,9- dimethyl - 9H- fluorenes -2- amine (27mmol), 1.13g tris(dibenzylideneacetone) dipalladium (0) (1.35mmol), 1.0mL tri-tert-butylphosphine (2.7mmol, 50% toluene solution), 4.8g sodium tert-butoxide (50mmol) and 125mL toluene are introduced into reaction vessel, and will mixing Object flows back 3 hours at 80 DEG C.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is logical Column chromatography purifying is crossed, 5.7g compound C-92 (yield: 34%) is obtained.The property of compound C-92 is shown in Table 1.
Example 8: prepare compound C-71
By 10g compound 2-1 (25mmol), 13.4g N- phenyl-[1,1 '-xenyl] -4- amine (55mmol), 2.3g tri- (dibenzalacetone) two palladium (0) (2.5mmol), 2mL tri-tert-butylphosphine (5mmol, 50% toluene solution), 9.6g sodium tert-butoxide (99mmol) and 260mL toluene are introduced into reaction vessel, and mixture is flowed back 3 hours at 80 DEG C.Reaction solution is cooling To room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 5.2g compound C-71 and (produce Rate: 18%).The property of compound C-71 is shown in Table 1.
Example 9: prepare compound C-93
Prepare compound 3-1
By 15g N- (9,9- dimethyl -9H- fluorenes -2- base) -11,11- dimethyl-N-(4- (naphthalene -2- base) phenyl) -11H- Benzo [b] fluorenes -2- amine (23mmol), 120mL dimethylformamide and 5.3g N-bromosuccinimide (30mmol) introduce anti- It answers in container, and mixture is stirred at room temperature overnight.With ethyl acetate diluting reaction solution and it is washed with distilled water.Then With the organic layer of the dry extraction of magnesium sulfate.Solvent is removed with Rotary Evaporators, products therefrom is purified by column chromatography, obtains 15g Compound 3-1 (yield: 89%).
Prepare compound C-93
By 10g compound 3-1 (14mmol), 2.7g diphenylamines (16mmol), 0.63g tris(dibenzylideneacetone) dipalladium (0) (0.68mmol), 0.5mL tri-tert-butylphosphine (1.4mmol, 50% toluene solution), 2.6g sodium tert-butoxide (28mmol) and 260mL toluene is introduced into reaction vessel, and mixture is flowed back 3 hours at 80 DEG C.Reaction solution is cooled to room temperature.With rotation Turn evaporimeter and remove solvent, and products therefrom is purified by column chromatography, obtains 3.1g compound C-93 (yield: 18%).Change The property for closing object C-93 is shown in Table 1.
Embodiment 10: prepare compound C-94
Prepare compound 4-1
By 26g 2- ([1,1 '-xenyl] -4- base) -11,11- dimethyl -11H- benzo [b] fluorenes (66mmol), 330mL Dimethylformamide, 200mL methylene chloride and 15.2g N-bromosuccinimide (85mmol) are introduced into reaction vessel, and will Mixture is stirred at room temperature overnight.With ethyl acetate diluting reaction solution and it is washed with distilled water.Then dry with magnesium sulfate The organic layer of extraction.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 26g compound 4-1 (yield: 83%).
Prepare compound C-94
By 13g compound 4-1 (27mmol), 9.9g N-1,1 '-xenyl -4- base -9,9- dimethyl -9H- fluorenes -2- amine (27mmol), 1.25g tris(dibenzylideneacetone) dipalladium (0) (1.4mmol), 1.1mL tri-tert-butylphosphine (2.7mmol, 50% first Benzole soln), 5.3g sodium tert-butoxide (54mmol) and 136mL toluene is introduced into reaction vessel, and mixture flowed back 3 at 80 DEG C Hour.Reaction solution is cooled to room temperature.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, is obtained To 4.5g compound C-94 (yield: 22%).The property of compound C-94 is shown in Table 1.
Example 11: prepare compound C-25
By 4g compound 1-4 (12mmol), 7.9g N- ([1,1 '-xenyl] -4- base) -9,9- dimethyl-N-(4 ' - (4,4,5,5- tetramethyls -1,3,2- dioxaborolan alkane -2- base)-[1,1 '-xenyl] -4- base) -9H- fluorenes -2- amine (12mmol), 0.72g tetrakis triphenylphosphine palladium (0.6mmol), 3.4g potassium carbonate (24mmol), 30mL toluene and 1 5mL ethyl alcohol It is introduced into reaction vessel, adds 15mL distilled water thereto, and mixture is stirred 18 hours at 80 DEG C.After the reaction was completed, Ethyl alcohol and toluene, and organic layer methylene chloride and distilled water extraction are removed with rotary evaporator.Then dry with magnesium sulfate Organic layer.Solvent is removed with Rotary Evaporators, and products therefrom is purified by column chromatography, obtains 3.1g compound C-25 and (produce Rate: 33%).The property of compound C-25 is shown in Table 1.
[table 1]
Device example 1: the OLED device of organic electroluminescent compounds of the manufacture comprising the disclosure
The OLED of following organic electroluminescent compounds of the manufacture comprising the disclosure.Successively use acetone, ethyl alcohol and distilled water To transparent electrode tin indium oxide (ITO) film (Ji Ao in the glass substrate for Organic Light Emitting Diode (OLED) device Horse, Japanese (Geomatec, Japan)) (10 Ω/sq) carry out ultrasonic washing, and are then stored in isopropanol.Then, will ITO substrate is mounted in the substrate holder of vacuum evapn phase depositing device.By N4, N4′Diphenyl-N4, N4′Bis- (9- phenyl- 9H- card azoles -3- base)-[1,1 '-xenyl] -4,4 '-diamines (compound HI-1) introduces the list of the vacuum phase deposition equipment In member, and then the pressure in the chamber of the equipment is controlled 10-6Support.Later, to the unit apply electric current so that The material of above-mentioned introducing evaporates, and the first hole injection layer with a thickness of 90nm is thus formed on ITO substrate.Then by Isosorbide-5-Nitrae, 5, - six nitrile (compound HI-2) of 8,9,12- six azepine triphenylene is introduced into another unit of the vacuum phase deposition equipment, and And evaporated and applying electric current to the unit, the second hole with a thickness of 5nm is thus formed on the first hole injection layer Implanted layer.Then by N- ([1,1 '-xenyl] -4- base) -9,9- dimethyl-N-(4- (9- phenyl -9H- card azoles -3- base) benzene Base) -9H- fluorenes -2- amine (compound HT-1) is introduced into another unit of the vacuum phase deposition equipment, and by described Unit applies electric current and evaporates, and the first hole transmission layer with a thickness of 10nm is thus formed on the second hole injection layer.It will change It closes object C-4 to be introduced into another unit of the vacuum phase deposition equipment, and is evaporated and applying electric current to the unit, Thus the second hole transmission layer with a thickness of 60nm is formed on the first hole transmission layer.Forming hole injection layer and hole biography After defeated layer, then following depositing light emitting layer.It is as follows, compound B-198 is introduced to a unit of vacuum phase deposition equipment It is middle to be used as main body, and compound D-71 is introduced into another unit as dopant.Two kinds of materials are evaporated with different rates And by the doping of based on the total amount of dopant and main body 2 weight % deposit on the second hole transmission layer formed with a thickness of The luminescent layer of 40nm.Then by bis- (9,9- dimethyl -9H- fluorenes -2- base) -6- (naphthalene -2- base) -1,3,5-triazines (chemical combination of 2,4- Object ET-1) and quinoline lithium (compound EI-1) be introduced into other two unit, and with 1: 1 rate evaporation and deposit with shine The electron transfer layer with a thickness of 35nm is formed on layer.Then, quinoline lithium (compound EI-1) conduct is deposited on the electron transport layer After the electron injecting layer of 2nm, by another vacuum phase deposition equipment, deposition thickness is on electron injecting layer The Al cathode of 80nm.Thus OLED device is manufactured.
The OLED device of manufacture is provided in brightness for driving voltage, luminous efficiency and the CIE chromaticity coordinates under 1,000 nits In the following table 2.
Device example 2 and 3: the OLED device of organic electroluminescent compounds of the manufacture comprising the disclosure
OLED device is manufactured in a manner of identical with device example 1, difference is to use compound shown in table 2 For the second hole transmission layer.
The OLED device of manufacture is provided in brightness for driving voltage, luminous efficiency and the CIE chromaticity coordinates under 1,000 nits In the following table 2.
Comparative example 1 to 3: OLED device of the manufacture comprising conventional organic electroluminescent compounds
OLED device is manufactured in a manner of identical with device example 1, difference is to use compound shown in table 2 For the second hole transmission layer.
The OLED device of manufacture is provided in brightness for driving voltage, luminous efficiency and the CIE chromaticity coordinates under 1,000 nits In the following table 2.
[table 2]
Second hole transmission layer Voltage (V) Efficiency (cd/A) Chromaticity coordinates (x) Chromaticity coordinates (y)
Device example 1 C-4 2.8 19.0 0.670 0.329
Device example 2 C-5 2.7 24.7 0.671 0.329
Device example 3 C-7 2.7 26.2 0.671 0.328
Comparative example 1 R-1 2.9 12.2 0.667 0.331
Comparative example 2 R-2 2.8 15.2 0.669 0.329
Comparative example 3 R-3 2.9 15.8 0.670 0.329
Device example 4 to 11: the OLED device of organic electroluminescent compounds of the manufacture comprising the disclosure
OLED device is manufactured in a manner of identical with device example 1, difference is to use compound shown in table 3 For the second hole transmission layer, and use based on compound B-199.
The OLED device of manufacture is provided in brightness for driving voltage, luminous efficiency and the CIE chromaticity coordinates under 1,000 nits In the following table 3.
Comparative example 4 and 5: OLED device of the manufacture comprising conventional organic electroluminescent compounds
OLED device is manufactured in a manner of identical with device example 4, difference is to use compound shown in table 3 For the second hole transmission layer.
The OLED device of manufacture is provided in brightness for driving voltage, luminous efficiency and the CIE chromaticity coordinates under 1,000 nits In the following table 3.
[table 3]
Second hole transmission layer Voltage (V) Efficiency (cd/A) Chromaticity coordinates (x) Chromaticity coordinates (y)
Device example 4 C-8 2.7 25.1 0.667 0.332
Device example 5 C-91 2.8 20.4 0.666 0.332
Device example 6 C-92 2.8 23.7 0.669 0.331
Device example 7 C-73 2.8 19.7 0.666 0.333
Device example 8 C-71 2.8 20.6 0.668 0.331
Device example 9 C-93 3.2 18.6 0.666 0.333
Device example 10 C-94 2.9 26.0 0.669 0.331
Device example 11 C-25 2.9 24.4 0.669 0.331
Comparative example 4 R-1 3.0 14.3 0.663 0.334
Comparative example 5 R-3 3.0 16.3 0.667 0.332
As shown in table 2 and 3, using according to the organic electroluminescent compounds of the disclosure in the second hole transmission layer Device has excellent luminous efficiency.Second hole transmission layer also acts as hole auxiliary layer or luminous auxiliary layer.
It can be seen that from result, the characteristic of device changes according to the position of substituent group, and whether it is fluorene structured in benzo [b] Second carbon potential or the bonding of the 5th carbon potential, even if it is also such that substituent group is identical.
In addition, using the compound of constitutional isomer relationship, root in comparison unit example 1 to 3 and comparative example 1 to 3 Have benzo [b] fluorene structured according to the organic electroluminescent compounds of the disclosure, wherein substituent group is bonded in the 5th carbon potential.Therefore, Since triplet energies increase, the luminous efficiency of device is improved, and since depositing temperature reduces, the thermal stability of device is excellent It is different, even if the molecular weight of these compounds is identical.This can be verified from the following table 4.
[table 4]

Claims (10)

1. a kind of organic electroluminescent compounds are indicated by following formula 1:
Wherein
Ar1To Ar6It each independently represents (C1-C30) alkyl for being substituted or being unsubstituted, be substituted or be unsubstituted (C6-C30) aryl, 5 to 30 unit's heteroaryls for being substituted or being unsubstituted or the spiral shell [fluorenes-(C3- for being substituted or being unsubstituted C30) cycloalkanes] base；Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6Monocycle or polycyclic 3 to 30 yuan of rouge can be connected to each other to form Ring race ring or aromatic ring, the hetero atom that (one or more) carbon atom can be selected from nitrogen, oxygen and sulphur by least one are replaced；
L1Indicate that singly-bound, (C6-C30) arlydene for being substituted or being unsubstituted or 5 to the 30 yuan of Asias for being substituted or being unsubstituted are miscellaneous Aryl；
L2Expression singly-bound, (C1-C30) alkylidene for being substituted or being unsubstituted, (C6-C30) the sub- virtue for being substituted or being unsubstituted Base or 5 to the 30 yuan of inferior heteroaryls for being substituted or being unsubstituted, condition are the L in the case where n is 02It is not present；
R1And R2Each independently represent hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted or without (C6-C30) aryl of substitution, 5 to 30 unit's heteroaryls for being substituted or being unsubstituted, (C3-C30) for being substituted or being unsubstituted Naphthenic base, 3 to 7 membered heterocycloalkyls for being substituted or being unsubstituted, (C6-C30) aryl (C1- for being substituted or being unsubstituted C30) alkyl ,-NR11R12、-SiR13R14R15、-SR16、-OR17, cyano, nitro or hydroxyl；Or it may be connected to (one or more) For adjacent substituents to form monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom can quilt At least one hetero atom for being selected from nitrogen, oxygen and sulphur is replaced；
R11To R17It each independently represents hydrogen, deuterium, halogen, (C1-C30) alkyl for being substituted or being unsubstituted, be substituted or not (C6-C30) aryl for being substituted is substituted or 5 to 30 unit's heteroaryls being unsubstituted, 3 to 7 yuan being substituted or being unsubstituted Heterocyclylalkyl or (C3-C30) naphthenic base for being substituted or being unsubstituted；Or may be connected to (one or more) adjacent substituents with Forming monocycle or polycyclic 3 to 30 yuan of aliphatic rings or aromatic ring, (one or more) carbon atom can be selected from by least one The hetero atom of nitrogen, oxygen and sulphur is replaced；
M indicates 1 to 2 integer, in the case where m is 2, NAr1Ar2Each of may be the same or different；
N indicates 0 to 2 integer, in the case where n is 2, NAr3Ar4Each of may be the same or different；
A indicates 1 to 5 integer, in the case where a is the integer of two or more, R1Each of may be the same or different；
B indicates 1 to 4 integer；In the case where b is the integer of two or more, R2Each of may be the same or different；
(Asia) heteroaryl contains at least one hetero atom for being selected from B, N, O, S, Si and P；And
The Heterocyclylalkyl contains at least one hetero atom for being selected from O, S and N.
2. organic electroluminescent compounds according to claim 1, wherein the compound indicated by formula 1 is by following formula 2 It is indicated with one in 3:
Wherein
Ar1To Ar6、L1、L2、R1、R2, a, b, m and n it is as defined in claim 1.
3. organic electroluminescent compounds according to claim 1, wherein in Ar1To Ar6、L1、L2、R1、R2And R11To R17 In described (Asia) alkyl being substituted, through described substituted (Asia) aryl, described (Asia) heteroaryl being substituted, described through taking The naphthenic base in generation, the Heterocyclylalkyl being substituted, the aryl alkyl being substituted and the spiral shell [fluorenes-(C3- being substituted C30) cycloalkanes] substituent group of base is each independently selected from least one of the group that is made up of: deuterium, halogen, cyanogen Base, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, halogenated (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio group, (C3-C30) naphthenic base, (C3-C30) cycloalkenyl, 3 to 7 membered heterocycloalkyls, (C6-C30) aryloxy group, (C6-C30) arylthio, 3 to 30 unit's heteroaryls, not for being unsubstituted or replacing through (C6-C30) aryl Be substituted or through 3 to 30 unit's heteroaryls replace (C6-C30) aryl, three (C1-C30) alkyl tin groups, alkyl silane groups, three (C6-C30) aryl Silylation, two (C1-C30) alkyl (C6-C30) aryl-silane bases, two (C6-C30) aryl-silane base of (C1-C30) alkyl, ammonia Base, list or two (C1-C30) alkyl aminos, list or two (C6-C30) arylaminos, (C1-C30) alkyl (C6-C30) aryl ammonia Base, (C1-C30) alkyl-carbonyl, (C1-C30) alkoxy carbonyl, (C6-C30) aryl carbonyl, two (C6-C30) aryl boryls, two (C1-C30) alkyl boryl, (C1-C30) alkyl (C6-C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl and (C1- C30) alkyl (C6-C30) aryl.
4. organic electroluminescent compounds according to claim 1, wherein
Ar1To Ar4Each independently represent (C6-C25) aryl for being substituted or being unsubstituted, 5 for being substituted or being unsubstituted are arrived 15 unit's heteroaryls or the spiral shell for being substituted or being unsubstituted [fluorenes-(C5-C8) cycloalkanes] base；
Ar5And Ar6It each independently represents (C1-C6) alkyl for being substituted or being unsubstituted or is substituted or is unsubstituted (C6-C12) aryl；Or monocycle or polycyclic 5 to 15 yuan of aliphatic rings or aromatic ring can be connected to each other to form；
L1Indicate that singly-bound, (C6-C20) arlydene for being substituted or being unsubstituted or 5 to the 15 yuan of Asias for being substituted or being unsubstituted are miscellaneous Aryl；
L2(C6-C12) arlydene for indicating singly-bound or being substituted or being unsubstituted, condition are the L in the case where n is 02It does not deposit ?；And
R1And R2Each independently represent hydrogen.
5. organic electroluminescent compounds according to claim 1, wherein
Ar1To Ar4Each independently represent (C6-C25) for being unsubstituted or replacing through (C1-C6) alkyl or (C6-C20) aryl Aryl；5 to 15 unit's heteroaryls for being unsubstituted or replacing through (C1-C6) alkyl or (C6-C12) aryl；The spiral shell being unsubstituted [fluorenes-pentamethylene] base；Or spiral shell [fluorenes-hexamethylene] base being unsubstituted；
Ar5And Ar6(C6-C12) aryl for each independently representing (C1-C6) alkyl being unsubstituted or being unsubstituted；But or that This connection is to form 5 to 15 yuan of aliphatic rings of monocycle；
L1Indicate singly-bound, (C6-C20) arlydene being unsubstituted or 5 to 15 yuan of inferior heteroaryls being unsubstituted；
L2(C6-C12) arlydene for indicating singly-bound or being unsubstituted, condition is in the case where n is 0, L2It is not present；And
R1And R2Each independently represent hydrogen.
6. organic electroluminescent compounds according to claim 1, wherein the compound indicated by formula 1 be selected from by with The group of lower composition:
7. a kind of hole mobile material includes organic electroluminescent compounds according to claim 1.
8. a kind of Organnic electroluminescent device includes organic electroluminescent compounds according to claim 1.
9. organic electro luminescent device according to claim 8 shines wherein the organic electroluminescent compounds are included in In at least one of layer and hole transmission layer layer.
10. a kind of display device includes organic electroluminescent compounds according to claim 1.
CN201780024400.8A 2016-05-03 2017-03-20 Organic electroluminescent compounds and organic electroluminescent device comprising the same Active CN109071413B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
KR10-2016-0054769 2016-05-03
KR20160054769 2016-05-03
KR10-2017-0024353 2017-02-23
KR1020170024353A KR20170124957A (en) 2016-05-03 2017-02-23 Organic electroluminescent compound and organic electroluminescent device comprising the same
PCT/KR2017/002959 WO2017191896A1 (en) 2016-05-03 2017-03-20 Organic electroluminescent compound and organic electroluminescent device comprising the same

Publications (2)

Publication Number Publication Date
CN109071413A true CN109071413A (en) 2018-12-21
CN109071413B CN109071413B (en) 2023-04-04

Family

ID=60386255

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780024400.8A Active CN109071413B (en) 2016-05-03 2017-03-20 Organic electroluminescent compounds and organic electroluminescent device comprising the same

Country Status (6)

Country Link
US (1) US10797243B2 (en)
EP (1) EP3452442B1 (en)
JP (1) JP6846438B2 (en)
KR (1) KR20170124957A (en)
CN (1) CN109071413B (en)
TW (1) TWI742071B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111662187A (en) * 2019-03-08 2020-09-15 江苏三月光电科技有限公司 Amino-containing organic compound and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110317184A (en) * 2018-03-29 2019-10-11 江苏三月光电科技有限公司 A kind of compound based on double dimethyl fluorenes, preparation method and applications
KR20210083158A (en) 2019-12-26 2021-07-06 롬엔드하스전자재료코리아유한회사 Organic electroluminescent compound and organic electroluminescent device comprising the same
KR102531630B1 (en) * 2020-11-19 2023-05-15 엘티소재주식회사 Compound and organic light emitting device including the same

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277626A (en) * 1998-09-09 2000-12-20 出光兴产株式会社 Organic electroluminescent device and phenylenediamine derivative
CN102082232A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Blue light organic electroluminescence device
WO2012039561A1 (en) * 2010-09-20 2012-03-29 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
US20120286247A1 (en) * 2011-05-11 2012-11-15 Samsung Mobile Display Co., Ltd. Condensed-cyclic compound, organic light-emitting device comprising the same, and flat panel display apparatus
WO2013012298A1 (en) * 2011-07-21 2013-01-24 Rohm And Haas Electronic Materials Korea Ltd. 9h-carbazole compounds and electroluminescent devices involving them
WO2014129846A1 (en) * 2013-02-21 2014-08-28 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and an organic electroluminescent device comprising the same
WO2015037965A1 (en) * 2013-09-16 2015-03-19 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2015061198A1 (en) * 2013-10-25 2015-04-30 E. I. Du Pont De Nemours And Company Blue luminescent compounds
WO2015084114A1 (en) * 2013-12-06 2015-06-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2015199493A1 (en) * 2014-06-27 2015-12-30 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2016021989A1 (en) * 2014-08-08 2016-02-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent devices comprising the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202013012401U1 (en) * 2012-07-23 2016-10-12 Merck Patent Gmbh Connections and Organic Electronic Devices
KR102420202B1 (en) 2014-06-27 2022-07-14 롬엔드하스전자재료코리아유한회사 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
KR102526212B1 (en) 2014-08-08 2023-04-28 롬엔드하스전자재료코리아유한회사 Organic electroluminescent compounds and organic electroluminescent devices comprising the same
KR101530885B1 (en) * 2015-02-27 2015-06-24 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102283231B1 (en) 2015-03-16 2021-07-30 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1277626A (en) * 1998-09-09 2000-12-20 出光兴产株式会社 Organic electroluminescent device and phenylenediamine derivative
CN102082232A (en) * 2010-09-16 2011-06-01 昆山维信诺显示技术有限公司 Blue light organic electroluminescence device
WO2012039561A1 (en) * 2010-09-20 2012-03-29 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device using the same
US20120286247A1 (en) * 2011-05-11 2012-11-15 Samsung Mobile Display Co., Ltd. Condensed-cyclic compound, organic light-emitting device comprising the same, and flat panel display apparatus
WO2013012298A1 (en) * 2011-07-21 2013-01-24 Rohm And Haas Electronic Materials Korea Ltd. 9h-carbazole compounds and electroluminescent devices involving them
WO2014129846A1 (en) * 2013-02-21 2014-08-28 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and an organic electroluminescent device comprising the same
WO2015037965A1 (en) * 2013-09-16 2015-03-19 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2015061198A1 (en) * 2013-10-25 2015-04-30 E. I. Du Pont De Nemours And Company Blue luminescent compounds
WO2015084114A1 (en) * 2013-12-06 2015-06-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2015199493A1 (en) * 2014-06-27 2015-12-30 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2016021989A1 (en) * 2014-08-08 2016-02-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent devices comprising the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111662187A (en) * 2019-03-08 2020-09-15 江苏三月光电科技有限公司 Amino-containing organic compound and application thereof

Also Published As

Publication number Publication date
US20190131526A1 (en) 2019-05-02
TW201808883A (en) 2018-03-16
EP3452442A1 (en) 2019-03-13
EP3452442B1 (en) 2021-02-17
TWI742071B (en) 2021-10-11
KR20170124957A (en) 2017-11-13
US10797243B2 (en) 2020-10-06
EP3452442A4 (en) 2019-12-25
CN109071413B (en) 2023-04-04
JP6846438B2 (en) 2021-03-24
JP2019515905A (en) 2019-06-13

Similar Documents

Publication Publication Date Title
CN105358654B (en) Organic electroluminescent compounds and Organnic electroluminescent device comprising the compound
JP7146880B2 (en) Hole-transporting material and organic electroluminescent device comprising the same
CN104768928B (en) Condensed fluoranthene compound, material for organic electroluminescent element using same, and organic electroluminescent element and electronic device using same
CN103313980B (en) Biscarbazole derivative and organic electroluminescent element using same
CN109996794A (en) Organic electroluminescent compounds and Organnic electroluminescent device comprising it
CN109451739A (en) Organic electroluminescent compounds and Organnic electroluminescent device including the organic electroluminescent compounds
CN105829279A (en) An organic electroluminescent compound and an organic electroluminescent device comprising the same
CN105764876A (en) Organic electroluminescent compound and organic electroluminescent device comprising the same
KR20210124149A (en) Organic Electroluminescent Compound and Organic Electroluminescent Device Comprising the Same
CN106604923A (en) Organic electroluminescent compounds and organic electroluminescent devices comprising the same
CN105189455A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN111148817A (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
TW201439277A (en) Organic electroluminescent compounds and an organic electroluminescent device comprising the same
CN106232591A (en) Electron transport material and the Organnic electroluminescent device comprising it
CN105408311A (en) Compound, organic electroluminescent element, and electronic device
CN103570737A (en) Heterocyclic compounds, organic light-emitting device comprising the same and organic light-emitting display
CN104995195A (en) Heterocyclic compound, material for organic electroluminescent element using same, and organic electroluminescent element and electronic device using same
CN108291140A (en) A variety of material of main parts and Organnic electroluminescent device comprising it
CN108779393B (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN105392789A (en) Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
CN109071413A (en) Organic electroluminescent compounds and Organnic electroluminescent device comprising it
CN105473569A (en) Compound, material for organic electroluminescent element, and electronic device
JP5640460B2 (en) Light emitting device and light emitting device material
CN109071556B (en) Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN108368120A (en) Organic electroluminescent compounds, electroluminescent organic material and the Organnic electroluminescent device comprising it

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant